U.S. patent number 10,604,654 [Application Number 15/951,577] was granted by the patent office on 2020-03-31 for curable resin composition.
This patent grant is currently assigned to SHIN-ETSU CHEMICAL CO., LTD.. The grantee listed for this patent is Shin-Etsu Chemical Co., Ltd.. Invention is credited to Takayuki Kusunoki, Yuusuke Takamizawa.
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United States Patent |
10,604,654 |
Kusunoki , et al. |
March 31, 2020 |
Curable resin composition
Abstract
One of the purposes of the present invention is to provide a
curable resin composition which has good curability and provides a
cured product having a sufficient hardness, in particular an
addition-curable organic silicon resin composition. The present
invention provides a curable resin composition comprising the
following components (A) to (C): (A) an organic-silicon compound
having at least two alkenyl groups in a molecule, (B) an organic
silicon compound which is represented by the formula (I) and has at
least three hydrosilyl groups each bonded to the carbon atom of the
benzene ring in an amount such that a ratio of the number of the
hydrosilyl group in component (B) to the number of the alkenyl
group in component (A) is 0.4 to 4, ##STR00001## and (C) a
hydrosilylation catalyst in a catalytic amount.
Inventors: |
Kusunoki; Takayuki (Annaka,
JP), Takamizawa; Yuusuke (Annaka, JP) |
Applicant: |
Name |
City |
State |
Country |
Type |
Shin-Etsu Chemical Co., Ltd. |
Tokyo |
N/A |
JP |
|
|
Assignee: |
SHIN-ETSU CHEMICAL CO., LTD.
(Tokyo, JP)
|
Family
ID: |
63791970 |
Appl.
No.: |
15/951,577 |
Filed: |
April 12, 2018 |
Prior Publication Data
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|
|
|
Document
Identifier |
Publication Date |
|
US 20180298150 A1 |
Oct 18, 2018 |
|
Foreign Application Priority Data
|
|
|
|
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Apr 13, 2017 [JP] |
|
|
2017-079831 |
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08K
5/5403 (20130101); C08G 77/52 (20130101); H01L
23/296 (20130101); H01L 33/56 (20130101); C08L
83/14 (20130101); C08L 83/14 (20130101); C08L
83/00 (20130101); C08K 5/56 (20130101); C08K
5/5403 (20130101); C08L 83/04 (20130101); H01L
33/507 (20130101); C08G 77/60 (20130101); C08G
77/20 (20130101); C07F 7/0805 (20130101); C08G
77/80 (20130101) |
Current International
Class: |
C08L
83/14 (20060101); C08K 5/54 (20060101); H01L
33/56 (20100101); H01L 23/29 (20060101); C08G
77/52 (20060101); C07F 7/08 (20060101); C08G
77/60 (20060101); H01L 33/50 (20100101); C08G
77/00 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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|
|
|
|
|
|
10-152615 |
|
Jun 1998 |
|
JP |
|
2001-064393 |
|
Mar 2001 |
|
JP |
|
2005-133073 |
|
May 2005 |
|
JP |
|
2006-093354 |
|
Apr 2006 |
|
JP |
|
5136963 |
|
Feb 2013 |
|
JP |
|
2015107978 |
|
Sep 2015 |
|
KR |
|
Other References
Machine translation of KR 2015107978 (no date). cited by examiner
.
Machine translation of JP 10-152615 (no date). cited by
examiner.
|
Primary Examiner: Zimmer; Marc S
Attorney, Agent or Firm: Birch, Stewart, Kolasch &
Birch, LLP
Claims
The invention claimed is:
1. A curable resin composition comprising the following components
(A) to (C): (A) an organic silicon compound having at least two
alkenyl groups in a molecule, (B) an organic silicon compound
represented by the following formula (1) in an amount such that a
ratio of the number of the hydrosilyl groups in component (B) to
the number of the alkenyl groups in component (A) is 0.4 to 4,
##STR00043## wherein R.sup.2 is, independently of each other, a
hydrogen atom or a monovalent hydrocarbon group having 1 to 12
carbon atoms and all of the X.sup.1 to X.sup.4 and X.sup.9 are a
group represented by the following formula (1'), ##STR00044##
wherein R.sup.2 is as defined above, and (C) a hydrosilylation
catalyst in a catalytic amount.
2. The curable resin composition according to claim 1, wherein
component (A) is an organic silicon compound represented by the
following formula (4):
(R.sup.4.sub.3SiO.sub.1/2).sub.a(R.sup.4.sub.2SiO.sub.2/2).sub.b(R.-
sup.4SiO.sub.3/2).sub.c(SiO.sub.4/2).sub.d(Y).sub.e(O.sub.1/2R.sup.3).sub.-
f (4), wherein R.sup.4 is, independently of each other, a
monovalent hydrocarbon group having 1 to 12 carbon atoms and
optionally having an unsaturated bond, provided that at least two
of R.sup.4 are an alkenyl group, R.sup.3 is a hydrogen atom or a
monovalent hydrocarbon group having 1 to 6 carbon atoms, a is an
integer of from 0 to 100, b is an integer of from 0 to 1,000, c is
an integer of from 0 to 500, d is an integer of from 0 to 500, e is
an integer of from 0 to 500, f is an integer of from 0 to 50, a
total of a, b, c, d and e is 2 to 1,000, and Y is a silphenylene
unit which has a valance of 1 to 26 and is represented by the
following formula (II), ##STR00045## wherein r is 0 or 1, k is an
integer of from 1 to 3, a bonding marked with ** in the formula
(II) bonds to a silicon atom of another siloxane in the formula
(4), R.sup.4 is as defined above, Z.sup.1 to Z.sup.9 are,
independently of each other, a hydrogen atom, a monovalent
hydrocarbon group having 1 to 6 carbon atoms, a divalent, trivalent
or tetravalent group represented by the following formula (5'), a
monovalent group represented by the following formula (5''), or a
group having a valance of 1 to 16 and represented by the following
formula (7'), R.sup.6 is, independently of each other, selected
from the groups defined for R.sup.4 or a group which has a valance
of 1 to 16 and is represented by the following formula (6'),
##STR00046## wherein a bonding marked with * in the formulas (5')
and (5'') bonds to a carbon atom of the benzene ring, a bonding
marked with ** in the formula (5') bonds to a silicon atom of
another siloxane in the formula (4), k is an integer of from 1 to
3, k' is an integer of from 1 to 3, R.sup.4 is as defined above,
and R.sup.5 is a monovalent hydrocarbon group having 1 to 6 carbon
atoms, ##STR00047## wherein Z' is, independently of each other, a
hydrogen atom, a monovalent hydrocarbon group having 1 to 6 carbon
atoms or the group represented by the formula (5') or (5''),
R.sup.4 is as defined above, a bonding marked with * in the formula
(7') bonds to a carbon atom of the benzene ring and a bonding
marked with *** in the formula (6') bonds to a silicon atom of
another siloxane in the formula (4).
3. A curable resin composition comprising the following components
(A) to (C): (A) an organic silicon compound having at least two
alkenyl groups in a molecule, (B) an organic silicon compound
represented by the following formula (2) in an amount such that a
ratio of the number of the hydrosilyl groups in component (B) to
the number of the alkenyl groups in component (A) is 0.4 to 4;
##STR00048## wherein R.sup.1 is, independently of each other, a
hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon
atoms or the group represented by the formula (4'), R.sup.2 is
independently of each other, a hydrogen atom or a monovalent
hydrocarbon group having 1 to 12 carbon atoms, X.sup.1 to X.sup.9
and X' are, independently of each other, a hydrogen atom, a
monovalent hydrocarbon group having 1 to 6 carbon atoms or the
group represented by the formula (1'), and at least two of X.sup.1
to X.sup.9 and X' are the group represented by the formula (1'),
and (C) a hydrosilylation catalyst in a catalytic amount.
4. A curable resin composition comprising the following components
(A) to (C): (A) an organic silicon compound having at least two
alkenyl groups in a molecule, (B) an organic silicon compound
represented by the following formula (3) in an amount such that a
ratio of the number of the hydrosilyl groups in component (B) to
the number of the alkenyl groups in component (A) is 0.4 to 4;
##STR00049## wherein R.sup.2 is, independently of each other, a
hydrogen atom or a monovalent hydrocarbon group having 1 to 12
carbon atoms, X.sup.1 to X.sup.4 and X.sup.9 are, independently of
each other, a hydrogen atom, a monovalent hydrocarbon group having
1 to 6 carbon atoms or the group represented by the formula (1') or
(3'), X' is, independently of each other, a hydrogen atom, a
monovalent hydrocarbon group having 1 to 6 carbon atoms or the
group represented by the formula (1'), at least two of X.sup.1 to
X.sup.4 and X.sup.9 are the group represented by the formula (3')
and at least two of X.sup.1 to X.sup.4, X.sup.9 and X' are the
group represented by the formula (1'), and (C) a hydrosilylation
catalyst in a catalytic amount.
5. A semiconductor device provided with a cured product obtained by
curing the curable resin composition according to claim 1 or 2.
6. The curable resin composition according to claim 3, wherein
component (A) is an organic silicon compound represented by the
following formula (4):
(R.sup.4.sub.3SiO.sub.1/2).sub.a(R.sup.4.sub.2SiO.sub.2/2).sub.b(R.-
sup.4SiO.sub.3/2).sub.c(SiO.sub.4/2).sub.d(Y).sub.e(O.sub.1/2R.sup.3).sub.-
f (4), wherein R.sup.4 is, independently of each other, a
monovalent hydrocarbon group having 1 to 12 carbon atoms and
optionally having an unsaturated bond, provided that at least two
of R.sup.4 are an alkenyl group, R.sup.3 is a hydrogen atom or a
monovalent hydrocarbon group having 1 to 6 carbon atoms, a is an
integer of from 0 to 100, b is an integer of from 0 to 1,000, c is
an integer of from 0 to 500, d is an integer of from 0 to 500, e is
an integer of from 0 to 500, f is an integer of from 0 to 50, a
total of a, b, c, d and e is 2 to 1,000, and Y is a silphenylene
unit which has a valance of 1 to 26 and is represented by the
following formula (II), ##STR00050## wherein r is 0 or 1, k is an
integer of from 1 to 3, a bonding marked with ** in the formula
(II) bonds to a silicon atom of another siloxane in the formula
(4), R.sup.4 is as defined above, Z.sup.1 to Z.sup.9 are,
independently of each other, a hydrogen atom, a monovalent
hydrocarbon group having 1 to 6 carbon atoms, a divalent, trivalent
or tetravalent group represented by the following formula (5'), a
monovalent group represented by the following formula (5''), or a
group having a valance of 1 to 16 and represented by the following
formula (7'), R.sup.6 is, independently of each other, selected
from the groups defined for R.sup.4 or a group which has a valance
of 1 to 16 and is represented by the following formula (6'),
##STR00051## wherein a bonding marked with * in the formulas (5')
and (5'') bonds to a carbon atom of the benzene ring, a bonding
marked with ** in the formula (5') bonds to a silicon atom of
another siloxane in the formula (4), k is an integer of from 1 to
3, k' is an integer of from 1 to 3, R.sup.4 is as defined above,
and R.sup.5 is a monovalent hydrocarbon group having 1 to 6 carbon
atoms, ##STR00052## wherein Z' is, independently of each other, a
hydrogen atom, a monovalent hydrocarbon group having 1 to 6 carbon
atoms or the group represented by the formula (5') or (5''),
R.sup.4 is as defined above, a bonding marked with * in the formula
(7') bonds to a carbon atom of the benzene ring and a bonding
marked with *** in the formula (6') bonds to a silicon atom of
another siloxane in the formula (4).
7. The curable resin composition according to claim 4, wherein
component (A) is an organic silicon compound represented by the
following formula (4):
(R.sup.4.sub.3SiO.sub.1/2).sub.a(R.sup.4.sub.2SiO.sub.2/2).sub.b(R.-
sup.4SiO.sub.3/2).sub.c(SiO.sub.4/2).sub.d(Y).sub.e(O.sub.1/2R.sup.3).sub.-
f (4), wherein R.sup.4 is, independently of each other, a
monovalent hydrocarbon group having 1 to 12 carbon atoms and
optionally having an unsaturated bond, provided that at least two
of R.sup.4 are an alkenyl group, R.sup.3 is a hydrogen atom or a
monovalent hydrocarbon group having 1 to 6 carbon atoms, a is an
integer of from 0 to 100, b is an integer of from 0 to 1,000, c is
an integer of from 0 to 500, d is an integer of from 0 to 500, e is
an integer of from 0 to 500, f is an integer of from 0 to 50, a
total of a, b, c, d and e is 2 to 1,000, and Y is a silphenylene
unit which has a valance of 1 to 26 and is represented by the
following formula (II), ##STR00053## wherein r is 0 or 1, k is an
integer of from 1 to 3, a bonding marked with ** in the formula
(II) bonds to a silicon atom of another siloxane in the formula
(4), R.sup.4 is as defined above, Z.sup.1 to Z.sup.9 are,
independently of each other, a hydrogen atom, a monovalent
hydrocarbon group having 1 to 6 carbon atoms, a divalent, trivalent
or tetravalent group represented by the following formula (5'), a
monovalent group represented by the following formula (5''), or a
group having a valance of 1 to 16 and represented by the following
formula (7'), R.sup.6 is, independently of each other, selected
from the groups defined for R.sup.4 or a group which has a valance
of 1 to 16 and is represented by the following formula (6'),
##STR00054## wherein a bonding marked with * in the formulas (5')
and (5'') bonds to a carbon atom of the benzene ring, a bonding
marked with ** in the formula (5') bonds to a silicon atom of
another siloxane in the formula (4), k is an integer of from 1 to
3, k' is an integer of from 1 to 3, R.sup.4 is as defined above,
and R.sup.5 is a monovalent hydrocarbon group having 1 to 6 carbon
atoms, ##STR00055## wherein Z' is, independently of each other, a
hydrogen atom, a monovalent hydrocarbon group having 1 to 6 carbon
atoms or the group represented by the formula (5') or (5''),
R.sup.4 is as defined above, a bonding marked with * in the formula
(7') bonds to a carbon atom of the benzene ring and a bonding
marked with *** in the formula (6') bonds to a silicon atom of
another siloxane in the formula (4).
8. A semiconductor device provided with a cured product obtained by
curing the curable resin composition according to claim 3 or 6.
9. A semiconductor device provided with a cured product obtained by
curing the curable resin composition according to claim 4 or 7.
Description
CROSS REFERENCE
This application claims the benefits of Japanese Patent Application
No. 2017-079831 filed on Apr. 13, 2017, the contents of which are
hereby incorporated by reference.
FIELD OF THE INVENTION
The present invention relates to a curable resin composition and a
semiconductor device provided with a cured product of the
composition. Specifically, the present invention relates to an
addition-curable organic silicon resin composition comprising an
organic silicon compound having a silphenylene skeleton and at
least three hydrosilyl groups in a molecule.
The addition-curable organic silicon resin composition has quick
curability and provides a cured product having an excellent heat
resistance and light resistance and, therefore, has been used as a
material for encapsulating semiconductor elements such as LEDs. For
instance, Japanese Patent No. 5136963, Patent literature 1,
describes an addition-curable silicone resin composition which
provides high adhesion to an LED package made of a thermoplastic
resin such as PPA. Japanese Patent Application Laid-Open No.
2006-93354, Patent literature 2, describes a method for
encapsulating an optical semiconductor element by compression
molding of an addition-curable silicone resin composition.
As described above, addition curable organic silicon resin
compositions are generally used as encapsulating materials for a
semiconductor, but the properties are not satisfactory. In
particular, in the field of encapsulating materials for a
semiconductor, a stress is applied to the encapsulating resin due
to external environment or a temperature rise during energization.
Therefore, a material having an excellent crack resistance is
required. However, crack resistance of the silicone resin is
insufficient and there is a problem that cracks occur easily in a
resin. In order to solve this problem, a soft silicone resin in the
form of a gel or a rubber is used. However, the gel or rubber
silicone resin is not suitable in the case of encapsulating a
semiconductor by compression molding or transfer molding, because
tackiness of the gel or rubber silicone resin is noticeable and,
thereby, sticking to a mold occurs. Therefore, a silicone resin is
required, which can withstand stresses while maintaining its
hardness enough to remove a mold from the resin.
Japanese Patent Application Laid-Open Nos. 2001-64393 and
2005-133073, herein referred to as Patent literatures 3 and 4,
describe that a silphenylene skeleton is incorporated in the resin
in order to provide toughness to a cured product while maintaining
its hardness. In these methods, the movement of the polymer chain
is restricted by the introduced silphenylene skeleton, whereby the
resin is made rigid and has high hardness.
PRIOR LITERATURES
Patent Literature 1: Japanese Patent No. 5136963
Patent Literature 2: Japanese Patent Application Laid-Open No.
2006-93354
Patent Literature 3: Japanese Patent Application Laid-Open No.
2001-64393
Patent Literature 4: Japanese Patent Application Laid-Open No.
2005-133073
SUMMARY OF THE INVENTION
The silphenylene has only two hydrosilyl groups bonded in the
aforesaid patent literatures, when such is use as a molding
material, the curing rate is too slow to attain sufficient
hardness, so that the productivity is inferior. Further,
silphenylene having only two hydrosilyl groups does not have a high
boiling point enough to be used as such. Therefore, the
silphenylene needs to be modified with a siloxane or an organic
substance by a condensation reaction or a hydrosilylation reaction
before used. The compound having the siloxane-modified silphenylene
skeleton has softness and brittleness due to the introduced
siloxane. The compound having the organic-modified silphenylene
skeleton has poor heat resistance and light resistance. Therefore,
these compounds are not suitable for an encapsulating material.
One of the purposes of the present invention is to provide a
curable resin composition which has good curability and provides a
cured product having a sufficient hardness. Specifically, the
purpose of the present invention is to provide an addition-curable
organic silicon resin composition.
The present inventors have made research and found that a curable
resin composition comprising an organic silicon compound having
three or more hydrosilyl groups and an organic silicon compound
having two or more alkenyl groups attains the aforesaid
purposes.
Thus, the present invention provides a curable resin composition
comprising the following components (A) to (C):
(A) an organic silicon compound having at least two alkenyl groups
in a molecule,
(B) an organic silicon compound represented by the following
formula (I) and having at least three hydrosilyl groups each bonded
to a carbon atom of the benzene ring in an amount such that a ratio
of the number of the hydrosilyl groups in component (B) to the
number of the alkenyl groups in component (A) is 0.4 to 4,
##STR00002## wherein n is 0 or 1, X.sup.1 to X.sup.9 are,
independently of each other, a hydrogen atom, a monovalent
hydrocarbon group having 1 to 6 carbon atoms or a group represented
by the following formula (1') or (3'), R.sup.1 is, independently of
each other, a hydrogen atom, a monovalent hydrocarbon group having
1 to 12 carbon atoms or a group represented by the following
formula (4'), and R.sup.2 is, independently of each other, a
hydrogen atom or a monovalent hydrocarbon group having 1 to 12
carbon atoms,
##STR00003## wherein R.sup.2 is as defined above and X' is,
independently of each other, a hydrogen atom, a monovalent
hydrocarbon atom having 1 to 6 carbon atoms, or the group
represented by the formula (1'), provided that at least two of the
groups represented by X.sup.1 to X.sup.9 and X' are the group
represented by the formula (1'), and
(C) a hydrosilylation catalyst in a catalytic amount.
Effects of the Invention
The present curable resin composition comprising an organic silicon
compound having three or more hydrosilyl groups reacts quickly to
form cross-link and, therefore, has excellent curability, compared
to an addition-curable organic silicon resin composition comprising
an organic silicon compound having only two hydrosilyl groups. The
cured product obtained from the present curable resin composition
has a silphenylene skeleton and, thereby, has a better hardness,
compared to a cured product obtained from an addition curable
composition which does not have a silphenylene skeleton.
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described below in detail.
(A) Alkenyl Group-Containing Organic Silicon Compound
Component (A) is an organic silicon compound having at least two
alkenyl groups in a molecule. The organic silicon compound may be
any known alkenyl group-containing organopolysiloxane
conventionally used in an addition reaction-curable siloxane resin
composition. The organic silicon compound may or may not have a
silphenylene skeleton. The organic silicon compound may be used
singly or in combination of two or more of them.
The component (A) is preferably represented by the following
formula (4):
(R.sup.4.sub.3SiO.sub.1/2).sub.a(R.sup.4.sub.2SiO.sub.2/2).sub.b(R.sup.4S-
iO.sub.3/2).sub.c(SiO.sub.4/2).sub.d(Y).sub.e(O.sub.1/2R.sup.3).sub.f
(4), wherein R.sup.4 is, independently of each other, a monovalent
hydrocarbon group having 1 to 12 carbon atoms and optionally having
an unsaturated bond, provided that at least two of R.sup.4 are an
alkenyl group, R.sup.3 is a hydrogen atom or a monovalent
hydrocarbon group having 1 to 6 carbon atoms, a is an integer of
from 0 to 100, b is an integer of from 0 to 1,000, c is an integer
of from 0 to 500, d is an integer of from 0 to 500, e is an integer
of from 0 to 500, f is an integer of from 0 to 50, a total of a, b,
c, d and e is 2 to 1,000, and Y is a silphenylene unit having a
valance of 1 to 26 and is represented by the following formula
(II),
##STR00004## wherein r is 0 or 1, k is an integer of from 1 to 3,
preferably 1, a bonding marked with ** in the formula (II) bonds to
a silicon atom of another siloxane in the formula (4), R.sup.4 is
as defined above, Z.sup.1 to Z.sup.9 are, independently of each
other, a hydrogen atom, a monovalent hydrocarbon group having 1 to
6 carbon atoms, a divalent, trivalent or tetravalent, preferably
divalent, group represented by the following formula (5'), a
monovalent group represented by the following formula (5''), or a
group having a valance of 1 to 16, preferably 1 to 3 and
represented by the following formula (7'), R.sup.6 is,
independently of each other, selected from the groups defined for
R.sup.4 or a group which has a valance of 1 to 16, preferably 1 to
3, and is represented by the following formula (6'),
##STR00005## wherein a bonding marked with * in the formulas (5')
and (5'') bond to a carbon atom of the benzene ring, a bonding
marked with ** in the formula (5') bonds to a silicon atom of
another siloxane in the formula (4), k is an integer of from 1 to
3, k' is an integer of from 1 to 3, R.sup.4 is as defined above,
and R.sup.5 is a monovalent hydrocarbon group having 1 to 6 carbon
atoms,
##STR00006## wherein Z' is, independently of each other, a hydrogen
atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms or
a group represented by the formula (5') or (5''), R.sup.4 is as
defined above, a bonding marked with * in the formula (7') bonds to
a carbon atom of the benzene ring and a bonding marked with *** in
the formula (6') bonds to a silicon atom of another siloxane in the
formula (4).
In the aforesaid formulas (6') and (7'), Z' is preferably a
hydrogen atom, or a monovalent hydrocarbon group having 1 to 6
carbon atoms. When the formulas (6') or (7') have a group
represented by the aforesaid formula (5'), one or two of Z' are
preferably the divalent group represented by the formula (5').
R.sup.4 is, independently of each other, a monovalent hydrocarbon
group having 1 to 12 carbon atoms which may have an unsaturated
bond, such as, for instance, a monovalent aliphatic saturated
hydrocarbon group having 1 to 12 carbon atoms such as alkyl groups
such as a methyl group, an ethyl group, a propyl group, a butyl
group, a hexyl group; cycloalkyl groups such as a cyclohexyl group,
a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms
such as aryl groups such as a phenyl group, a tolyl group, a xylyl
group and a naphthyl group and aralkyl groups such as a benzyl
group, a phenylethyl group and a phenylpropyl group, and alkenyl
groups such as a vinyl group, an allyl group and a propenyl group.
At least two of R.sup.4 are an alkenyl group. The alkenyl group is
preferably a vinyl group. R.sup.4 which is not an alkenyl group is
preferably a methyl group or a phenyl group. R.sup.3 is a hydrogen
atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms,
such as, for instance, a monovalent aliphatic saturated hydrocarbon
group such as alkyl groups such as a methyl group, an ethyl group,
a propyl group, a butyl group and a hexyl group and cycloalkyl
groups such as a cyclohexyl group, and a phenyl group. Among these,
a hydrogen atom, a methyl group and an ethyl group are
preferable.
Component (A) preferably has 0.005 to 0.5 mol, particularly 0.01 to
0.2 mol, of the alkenyl group, in 100 g of component (A). The
alkenyl group may be present on R.sup.4.sub.3SiO.sub.1/2 unit,
R.sup.4.sub.2SiO.sub.2/2 unit, and/or R.sup.4SiO.sub.3/2 unit,
preferably on R.sup.4.sub.3SiO.sub.1/2 unit.
a is an integer of from 0 to 100, preferably 0 to 75, further
preferably 0 to 50. b is an integer of from 0 to 1,000, preferably
0 to 800, more preferably 0 to 500, further preferably 0 to 250. c
is an integer of from 0 to 500, preferably 0 to 250, more
preferably 0 to 125. d is an integer of from 0 to 500, preferably 0
to 250, more preferably 0 to 125. e is an integer of from 0 to 500,
preferably 0 to 250, more preferably 0 to 125. f is an integer of
from 0 to 50, preferably 0 to 40, more preferably 0 to 30. A total
of a, b, c, d and e is 2 to 1,000, preferably 5 to 750, further
preferably 10 to 500. k is an integer of from 1 to 3, preferably
1.
Component (A) preferably comprises at least one branched
organopolysiloxane. In the branched organopolysiloxane, a total of
c and d in the foresaid formula is preferably in the range of 5 to
750, further preferably 10 to 500. Further, preferred is a
combination of the branched organopolysiloxane and the linear
organopolysiloxane. A mass ratio of the branched organopolysiloxane
to the linear organopolysiloxane is preferably 100:5 to 100:100,
more preferably 100:10 to 100:50.
The organic silicon compound may be one produced by a known method
or a commercially available product.
Y is a silphenylene unit having a valance of 1 to 26, preferably 1
to 12, and represented by the following formula (II). The group
represented by the formula (II) is preferably such represented by
the following formula (5), (6) or (7).
[Group Represented by the Following Formula (5)]
##STR00007## wherein Z.sup.1 to Z.sup.4 and Z.sup.9 are,
independently of each other, a hydrogen atom, a monovalent
hydrocarbon group having 1 to 6 carbon atoms, a divalent, trivalent
or tetravalent, preferably divalent, group, represented by the
formula (5'), a monovalent group represented by the formula (5''),
R.sup.4, k and k' are as defined above. k is preferably 1. At least
one of Z.sup.1 to Z.sup.4 and Z.sup.9 is preferably the group
represented by the formula (5') or (5''). In particular, at least
two of Z.sup.1 to Z.sup.4 and Z.sup.9 are the divalent group
represented by the aforesaid formula (5').
##STR00008##
Examples of the group represented by the formula (5) include the
group represented by the following formula.
##STR00009## [Group Represented by the Following Formula (6)]
##STR00010## wherein R.sup.6 is, independently of each other,
selected from the groups defined for R.sup.4 or a group having a
valance of 1 to 16, preferably 1 to 3, which is represented by the
following formula (6'). R.sup.4 and k are as defined above. k is
preferably 1. Z.sup.1 to Z.sup.9 and Z' are, independently of each
other, a hydrogen atom, a monovalent hydrocarbon group having 1 to
6 carbon atoms, a divalent, trivalent or tetravalent, preferably
divalent, group represented by the formula (5'), or a monovalent
group represented by the formula (5''). At least one of Z.sup.1 to
Z.sup.9 are preferably a divalent group represented by the formula
(5'). The rest of Z.sup.1 to Z.sup.9 is preferably, independently
of each other, a hydrogen atom or a monovalent hydrocarbon group
having 1 to 6 carbon atoms, further preferably a hydrogen atom.
R.sup.6 is preferably, a methyl group or a group represented by the
formula (6'). In the formula (6'), Z' is as defined above,
preferably a hydrogen atom.
##STR00011##
Examples of the group represented by the formula (6) include the
group represented by the following formula.
##STR00012## [Group Represented by the Following Formula (7)]
##STR00013## wherein Z.sup.1 to Z.sup.4 and Z.sup.9 are,
independently of each other, a hydrogen atom, a monovalent
hydrocarbon group having 1 to 6 carbon atoms, or a group
represented by the following formula (7'), Z' is, independently of
each other, a hydrogen atom, a monovalent hydrocarbon group having
1 to 6 carbon atoms, a group represented by the formula (5'), or a
group represented by the formula (5''), provided that at least two
of Z to Z.sup.4 and Z.sup.9 are the group represented by the
following formula (7'). R.sup.4 and k are as defined above. k is
preferably 1. At least one of Z.sup.1 to Z.sup.9 and Z' is
preferably the divalent group represented by the aforesaid formula
(5').
##STR00014##
Examples of the group represented by the formula (7) include the
group represented by the following formula.
##STR00015##
Examples of the monovalent hydrocarbon group having 1 to 6 carbon
atoms in the formulas (5) to (7) include a monovalent aliphatic
saturated hydrocarbon group such as an alkyl group such as a methyl
group, an ethyl group, a propyl group, a butyl group, and a hexyl
group and a cycloalkyl group such as a cyclohexyl group, and a
phenyl group. Among these, a methyl group and an ethyl group are
preferable.
[(B) Organic Silicon Compound Having at Least Three Hydrosilyl
Groups]
Component (B) is the organic silicon compound which has at least
three hydrosilyl groups each bonded to a carbon atom of the benzene
ring and represented by the following formula (I).
##STR00016## wherein n is 0 or 1, X.sup.1 to X.sup.9 are,
independently of each other, a hydrogen atom, a monovalent
hydrocarbon group having 1 to 6 carbon atoms or a group represented
by the following formula (1') or (3'), R.sup.1 is, independently of
each other, a hydrogen atom, a monovalent hydrocarbon group having
1 to 12 carbon atoms or a group represented by the following
formula (4'), and R.sup.2 is, independently of each other, a
hydrogen atom or a monovalent hydrocarbon group having 1 to 12
carbon atoms,
##STR00017## wherein R.sup.2 is as defined above and X' is,
independently of each other, a hydrogen atom, a monovalent
hydrocarbon atom having 1 to 6 carbon atoms, or the group
represented by the formula (1'), provided that at least two of the
groups represented by X.sup.1 to X.sup.9 and X' are the group
represented by the formula (1').
The monovalent hydrocarbon group having 1 to 12 carbon atoms is
preferably a hydrocarbon group which does not have an aliphatic
unsaturated bond, such as alkyl groups such as a methyl group, an
ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl
group and an octyl group; cycloalkyl groups such as a cyclohexyl
group; aryl groups such as a phenyl group, a tolyl group, a xylyl
group and a naphthyl group; aralkyl groups such as a benzyl group,
a phenylethyl group and a phenylpropyl group. R.sup.2 is preferably
a methyl group.
Examples of a monovalent hydrocarbon group having 1 to 6 carbon
atoms in the groups X.sup.1 to X.sup.9 and X' include alkyl groups
such as a methyl group, an ethyl group, a propyl group, a butyl
group, and a hexyl group, cycloalkyl groups such as a cyclohexyl
group, and a phenyl group. X.sup.1 to X.sup.9 and X' are preferably
a hydrogen atom or a group represented by the aforesaid formula
(1').
Preferred are compounds represented by the following formula (1),
(2) or (3).
[Compound Represented by the Following Formula (1)]
##STR00018## wherein R.sup.2 is as defined above, X.sup.1 to
X.sup.4 and X.sup.9 are, independently of each other, a hydrogen
atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms or
a group represented by the formula (1'), and at least two of
X.sup.1 to X.sup.4 and X.sup.9 are the group represented by the
formula (1'). X.sup.1 to X.sup.4 and X.sup.9 are preferably a
hydrogen atom or the group represented by the aforesaid formula
(1'). The all of the X.sup.1 to X.sup.4 and X.sup.9 may be the
group represented by the formula (1').
Examples of the compound represented by the formula (1) include
organic silicon compounds represented by the following
formulas.
##STR00019## [Compound Represented by the Following Formula
(2)]
##STR00020## wherein R.sup.1 is, independently of each other, a
hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon
atoms or the group represented by the formula (4'), R.sup.2 is as
defined above, X.sup.1 to X.sup.9 and X' are, independently of each
other, a hydrogen atom, a monovalent hydrocarbon group having 1 to
6 carbon atoms or a group represented by the formula (1'), and at
least two of X.sup.1 to X.sup.9 and X' are the group represented by
the formula (1'). Preferred are a compound wherein at least one of
R.sup.1 is a group represented by the formula (4') and the other
R.sup.1 is a hydrogen atom or a monovalent hydrocarbon group having
1 to 12 carbon atoms, a compound wherein both of R.sup.1 are the
groups represented by the formula (4'), and a compound wherein both
of R.sup.1 is a monovalent hydrocarbon group having 1 to 12 carbon
atoms. Further, X.sup.1 to X.sup.9 and X' are preferably a hydrogen
atom or the group represented by the formula (1'). All of the
X.sup.1 to X.sup.9 and X' may be the group represented by the
formula (1').
Examples of the compound represented by the formula (2) include
organic silicon compounds represented by the following
formulas.
##STR00021## [Compound Represented by the Following Formula
(3)]
##STR00022## wherein R.sup.2 is as defined above, X.sup.1 to
X.sup.4 and X.sup.9 are, independently of each other, a hydrogen
atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms or
a group represented by the formula (1') or (3'), and X' is,
independently of each other, a hydrogen atom, a monovalent
hydrocarbon group having 1 to 6 carbon atoms or a group represented
by the formula (1'), provided that at least two of X.sup.1 to
X.sup.4 and X.sup.9 are the group represented by the formula (3').
Preferably, the residues, X.sup.1 to X.sup.4 and X.sup.9 and X',
are a hydrogen atom or the group represented by the formula (1'),
and at least two of X.sup.1 to X.sup.4 and X.sup.9 are the group
represented by the formula (1').
An Example of the compound represented by the formula (3) is
organic silicon compounds represented by the following formula.
##STR00023##
The present component (B) has at least three hydrogen atoms each
bonded to a silicon atom, i.e., SiH groups. Preferably, component
(B) has 0.15 to 3 mols, more preferably 0.3 to 1.5 mols, of SiH
groups in 100 g of component (B).
An amount of component (B) is such that a ratio of the number of
the hydrogen atoms each bonded to the silicon atom, i.e. hydrosilyl
groups, in component (B) to the number of the alkenyl groups in
component (A) is 0.4 to 4, preferably 0.6 to 2.5, further
preferably 0.8 to 2.2. If the amount is less than the
aforementioned lower limit, the amount of SiH group is insufficient
so that curing does not proceed satisfactorily. If the amount
exceeds the aforementioned upper limit, unreacted SiH groups cause
a side reaction such as dehydrogenation, which is not preferred.
When the composition comprises component (D) described below, the
amount of component (B) may be such that a ratio of the total
number of the hydrosilyl groups in components (B) and (D) to the
number of the alkenyl groups in component (A) is in the aforesaid
range.
Component (B) may be used singly or two or more in combination.
Component (B) may be one produced by any known method or a
commercially available product.
[(C) Hydrosilylation Catalyst]
Component (C) is a hydrosilylation catalyst which promotes the
addition reaction of the alkenyl group of component (A) with the
hydrosilyl group of component (B). Any known catalyst may be used
and not particularly limited. Preferred is a catalyst selected from
an element of the platinum group metals and a compound including an
element of the platinum group metals. Examples of these catalysts
include platinum catalysts such as platinum, including platinum
black, platinum chloride, a chloroplatinic acid, a complex of
platinum with an olefin such as a complex of platinum with a
divinylsiloxane, and a complex of a platinum with a carbonyl;
palladium catalysts; and rhodium catalysts. The catalyst may be
used singly or in combination of them. Preferred are chloroplatinic
acid and a complex of platinum with an olefin such as a complex of
platinum with divinylsiloxane.
Component (C) may be used in a catalytic amount. The catalytic
amount is such as to accelerate the hydrosilylation of components
(A) and (B) and may properly be decided, depending on a desired
curing rate. For instance, when a platinum group metal catalyst is
used, the amount, reduced to a platinum group metal, is preferably
0.1 to 50 ppm, more preferably 1 to 10 ppm, relative to the total
mass of the composition, in view of reactivity.
[(D) Organic Silicon Compound Having Two Hydrogen Atoms Each Bonded
to a Silicon Atom]
The present curable resin composition may comprise an organic
silicon compound having two hydrogen atoms each bonded to a silicon
atom, together with component (B), in order to control the
crosslink density. Component (D) may be one produced by any known
method or a commercially available product. The hydrogen atoms each
bonded to a silicon atom is preferably at the both terminals of a
linear organic silicon compound such as one represented by the
following formula (8) or (9).
(R.sup.4.sub.2HSiO.sub.1/2).sub.2(R.sup.4.sub.2SiO.sub.2/2).sub.q(W).sub.-
h (8)
wherein R.sup.4 is a monovalent hydrocarbon group having 1 to 12
carbon atoms, W is a substituent represented by the following
general formula (8'), g is an integer of from 0 to 50, h is an
integer of from 0 to 50, and a total of g and h is 1 to 50.
##STR00024##
wherein R.sup.4 is as defined above, v is an integer of from 0 to
3.
##STR00025##
wherein R.sup.4 is as defined above, v' is an integer of from 0 to
3.
In the formulas (8) and (9), R.sup.4 is a monovalent hydrocarbon
group having 1 to 12 carbon atoms, such as, for instance, a
monovalent aliphatic saturated hydrocarbon group having 1 to 12
carbon atoms, such as alkyl groups such as a methyl group, an ethyl
group, a propyl group, a butyl group and a hexyl group, and
cycloalkyl groups such as a cyclohexyl group; and a monovalent
aromatic hydrocarbon group having 6 to 12 carbon atoms such as aryl
groups such as phenyl, tolyl, xylyl and naphthyl groups; aralkyl
groups such as a benzyl group, a phenylethyl group and a
phenylpropyl group. A methyl group and a phenyl group are
preferable.
Component (D) has the hydrogen atoms each bonded to a silicon atom,
i.e. SiH groups, at both terminals of the linear organosiloxane.
Component (D) preferably has 0.005 to 0.5 mol, more preferably 0.01
to 0.2 mol, of SiH groups, in 100 g of component (D).
g is an integer of from 0 to 50, preferably 0 to 25, further
preferably 0 to 10. h is an integer of from 0 to 50, preferably 0
to 10, more preferably 0 to 5. A total of g and h is 1 to 50,
preferably 1 to 25, further preferably 1 to 10. v is an integer of
from 0 to 3, preferably 0 or 1. v' is an integer of from 0 to 3,
preferably 0 or 1.
The compounding ratio of components (B) to (D) may be in a range
where the component (B) does not impair the effect of improving the
curing rate. Preferably, a percentage of component (B) is 10 to
100%, more preferably 25 to 100%, further preferably 50 to 100%,
relative to a total mass of components (B) and (D).
The present curable silicon resin composition may further comprise
other additives such as a fluorescent material, an inorganic
filler, an adhesion-imparting agent, and a curing inhibitor in
addition to components (A) to (D), if needed. Each of component
will be explained below in detail.
Fluorescent Material
The present fluorescent material is not particularly limited and
any conventional fluorescent material may be used. For instance,
preferred is such that absorbs light generated by a light-emitting
semiconductor diode having a semiconductor element as a light
emitting layer, in particular a nitride semiconductor element, and
converts a wavelength of the absorbed light. The fluorescent
material is preferably selected from, for instance, the group
consisting of nitride fluorescent materials and oxynitride
fluorescent materials which are activated mainly by lanthanide
elements such as Eu and Ce; alkaline earth metal halogen apatite,
alkaline earth metal borate halogen, alkaline earth metal
aluminate, alkaline earth metal silicate, alkaline earth metal
sulfide, alkaline earth metal thiogallate, alkaline earth metal
silicon nitride and germinate fluorescent materials activated
mainly by lanthanide elements such as Eu or by transition metal
elements such as Mn; rare earth metal aluminate and rare earth
metal silicate fluorescent materials which are activated mainly by
lanthanide elements such as Ce; organic fluorescent materials and
organic complex fluorescent materials which are activated mainly by
lanthanide elements such as Eu; and Ca--Al--Si--O--N type
oxynitride glass fluorescent materials.
Examples of the nitride fluorescent materials which are activated
mainly by lanthanide elements such as Eu and Ce include
M.sub.2Si.sub.5N.sub.8:Eu, MSi.sub.7N.sub.10:Eu,
M.sub.1.8Si.sub.5O.sub.0.2N.sub.8:Eu, and
M.sub.0.9Si.sub.7O.sub.0.1N.sub.10:Eu, wherein M is at least one
selected from the group consisting of Sr, Ca, Ba, Mg and Zn.
Examples of the oxynitride fluorescent materials which are
activated mainly by lanthanide elements such as Eu and Ce include
MSi.sub.2O.sub.2N.sub.2:Eu, wherein M is at least one selected from
the group consisting of Sr, Ca, Ba, Mg and Zn.
Examples of the alkaline earth metal halogen apatite fluorescent
materials which are activated mainly by lanthanide elements such as
Eu or transition metal elements such as Mn include
M.sub.5(PO.sub.4).sub.3X:R', wherein M is at least one selected
from the group consisting of Sr, Ca, Ba, Mg and Zn, X is at least
one selected from the group consisting of F, Cl, Br and I, and R'
is at least one of Eu and Mn.
Examples of the alkaline earth metal halogen borate fluorescent
materials include M.sub.2B.sub.5O.sub.9X:R', wherein M is at least
one selected from the group consisting of Sr, Ca, Ba, Mg and Zn, X
is at least one selected from the group consisting of F, Cl, Br and
I, and R' is at least one of Eu and Mn.
Examples of the alkaline earth metal aluminate fluorescent
materials include SrAl.sub.2O.sub.4:R',
Sr.sub.4Al.sub.14O.sub.25:R', CaAl.sub.2O.sub.4:R',
BaMg.sub.2Al.sub.16O.sub.27:R', BaMg.sub.2Al.sub.16O.sub.12:R' and
BaMgAl.sub.10O.sub.17:R', wherein R' is at least one of Eu and
Mn.
Examples of the alkaline earth metal sulfide fluorescent materials
include La.sub.2O.sub.2S:Eu, Y.sub.2O.sub.2S:Eu and
Gd.sub.2O.sub.2S:Eu.
Examples of the rare earth metal aluminate fluorescent materials
which are activated mainly by lanthanide elements such as Ce
include YAG type fluorescent materials represented by compositional
formulas: Y.sub.3Al.sub.5O.sub.12:Ce,
(Y.sub.0.8Gd.sub.0.2).sub.3Al.sub.5O.sub.12:Ce, Y.sub.3
(Al.sub.0.8Ga.sub.0.2).sub.5O.sub.12:Ce, and
(Y,Gd).sub.3(Al,Ga).sub.5O.sub.12 and those compounds where a part
or the whole of Y are replaced with Tb or Lu, such as
Tb.sub.3Al.sub.5O.sub.12:Ce and Lu.sub.3Al.sub.5O.sub.12:Ce.
Examples of other fluorescent materials include ZnS:Eu,
Zn.sub.2GeO.sub.4:Mn and MGa.sub.2S.sub.4:Eu, wherein M is at least
one selected from the group consisting of Sr, Ca, Ba, Mg and
Zn.
The aforementioned fluorescent materials may comprise at least one
selected from the group consisting of Tb, Cu, Ag, Au, Cr, Nd, Dy,
Co, Ni and Ti, in place of Eu or in addition to Eu, if needed.
The Ca--Al--Si--O--N type oxynitride glass fluorescent material
comprises, as a matrix, oxynitride glass comprising 20 to 50 mole %
of CaCO.sub.3, calculated as CaO, 0 to 30 mole % of
Al.sub.2O.sub.3, 25 to 60 mole % of SiO, 5 to 50 mole % of AlN and
0.1 to 20 mole % of rare earth metal oxides or transition metal
oxides, wherein the total amount of the aforesaid components is 100
mole %. The fluorescent material with the oxynitride glass matrix
preferably comprises nitrogen atoms in an amount of 15 mole % or
less and preferably comprises, besides rare earth metal oxides
ions, the other rare earth metal ions, as a co-activator, which
work as a sensitizer in an amount of 0.1 to 10 mole %, calculated
as rare earth metal oxides, in the fluorescent glass.
Other fluorescent materials which have a similar function and
provide similar effects may be used.
The fluorescent material preferably has a mean diameter of 10 nm or
more, more preferably 10 nm to 10 .mu.m, further preferably 10 nm
to 1 .mu.m. The mean diameter is determined from a particle size
distribution obtained in a laser diffraction method using a Cilas
laser measurement instrument.
An amount of the fluorescent materials is preferably 0.1 to 2,000
parts by mass, more preferably 0.1 to 100 parts by mass, relative
to 100 parts by mass of the components other than the fluorescent
material, for instance, 100 parts by mass of components (A) to (C)
and optionally component (D). When the present cured product is
used as a wavelength conversion film comprising a fluorescent
material, the amount of the fluorescent material is preferably 10
to 2,000 parts by mass.
Inorganic Filler
Examples of the inorganic filler include silica, fumed silica,
fumed titanium dioxide, alumina, calcium carbonate, calcium
silicate, titanium dioxide, iron (III) oxide and zinc oxide. The
inorganic filler may be used singly or in combination of two or
more of them.
An amount of the inorganic filler may be 20 parts by mass or less,
preferably 0.1 to 10 parts by mass, relative to total 100 parts by
mass of components (A) to (C) and optionally component (D), but not
limited to these.
Adhesion-Imparting Agent
The present curable resin composition may comprise an
adhesion-imparting agent in order to add adhesiveness to a cured
product, if needed. Examples of the adhesion-imparting agent
include organosiloxane oligomers having at least one selected from
a hydrogen atom bonded to a silicon atom and an alkenyl group, and
at least one selected from a hydroxysilyl group, an alkoxy group,
an epoxy group or a nitrogen atom-containing substituent. The
organosiloxane oligomer preferably has 4 to 50 silicon atoms, more
preferably 4 to 20 silicon atoms. This organosiloxane oligomer is
different from component (A) in that the former has a hydroxysilyl
group, an alkoxy group, an epoxy group or a nitrogen
atom-containing substituent.
The adhesion-imparting agent may be organooxysilyl-modified
isocyanurate represented by the following general formula (10) or
its hydrolysis and condensation product, i.e.,
organosiloxane-modified isocyanurate.
##STR00026##
In formula (10), R.sup.7 is, independently of each other, an
organic group represented by the following formula (11) or a
monovalent, unsaturated aliphatic hydrocarbon group which may
comprise an oxygen atom, provided that at least one of R.sup.7 is
the group represented by the formula (11).
##STR00027##
wherein R.sup.8 is a hydrogen atom or a monovalent hydrocarbon
group having 1 to 6 carbon atoms, such as a methyl or ethyl group,
and e is an integer of from 1 to 6, preferably 1 to 4.
The monovalent, unsaturated aliphatic hydrocarbon group is
preferably a linear or branched alkenyl group having 2 to 8 carbon
atoms, further preferably 2 to 6 carbon atoms, such as a vinyl
group, an allyl group, a 1-butenyl group, a 1-hexenyl group, a
2-methylpropenyl group and a (meth)acryl group.
An amount of the adhesion-imparting agent is preferably 10 parts by
mass or less, more preferably 0.1 to 8 parts by mass, further
preferably 0.2 to 5 parts by mass, relative to total 100 parts by
mass of components (A) to (C) and optionally component (D). When
the amount of the adhesion-imparting agent is within the aforesaid
range, the effect of the present invention is not obstructed and
the adhesive property is improved.
The amount of the adhesion-imparting agent is preferably such that
a ratio of the total number of hydrosilyl groups in the composition
to the total number of alkenyl groups in the composition is 0.4 to
4, more preferably 0.6 to 3, further preferably 0.8 to 2.
Curing Inhibitor
The present curable resin composition may further comprise a curing
inhibitor in order to suppress the reactivity to improve storage
stability. Examples of the curing inhibitor include
triallylisocyanurate, alkyl maleates, acetylene alcohols,
silane-modified or siloxane-modified product of these,
hydroperoxides, tetramethylethylenediamine, benzotriazole and a
mixture of them.
An amount of the curing inhibitor is preferably 0.001 to 1 part by
mass, further preferably 0.005 to 0.5 part by mass, relative to the
total 100 parts by mass of components (A) to (C) and optionally
component (D).
Other Additives
The present curable resin composition may comprise other additives
besides the aforesaid components. Examples of the other additives
include anti-aging agents, radical polymerization inhibitors, flame
retardants, surfactants, antiozonants, light stabilizers,
thickeners, plasticizers, antioxidants, heat stabilizers,
electrical conductivity-imparting agents, antistatic agents,
radiation insulating agents, nucleating agents, phosphorus-type
peroxide decomposers, lubricants, pigments, metal-inactivating
agents, physical property-adjusting agents and organic solvents.
These optional components may be used singly or in combination of
two or more of them.
The simplest embodiment of the present curable resin composition
consists of components (A), (B) and (C). In particular, it is
preferred that the composition does not comprise any inorganic
filler such as silica, in order to prepare a cured product having
high transparency. The inorganic filler is as described above.
The present curable resin composition may be prepared in any known
manners. For instance, the composition may be prepared by mixing
component (A), component (B), component (C) and the other optional
components in any manner. For instance, the aforesaid components
are placed in a commercial stirrer, such as THINKY CONDITIONING
MIXER, ex Thinky Corporation, and mixed homogeneously for about 1
to 5 minutes to prepare the present curable resin composition.
The present curable resin composition may be cured in any known
manners. Curing conditions are not particularly limited. For
instance, the composition may be cured at 60 to 180 degrees C. for
1 to 12 hours. In particular, the composition is cured stepwise.
The stepwise curing preferably consists of the following two steps.
The curable resin composition is first heated at 60 to 100 degrees
C. for 0.5 to 2 hours to be defoamed sufficiently. Subsequently,
the composition is heated at 120 to 180 degrees C. for 1 to 10
hours to cure. Through these steps, the composition is sufficiently
cured, no bubble occur and the cured product is colorless and
transparent, even when a cured product has a large thickness. In
the present specification, "colorless and transparent" means that a
light transmittance at 450 nm of a cured product having a thickness
of 1 mm is 80% or more, preferably 85% or more, particularly
preferably 90% or more.
The curable resin composition provides a cured product having a
high optical transparency. Accordingly, the present silicone
composition is useful as an encapsulating material for LED
elements, in particular blue LED elements and violet LED elements.
The encapsulation of LED elements with the present silicone
composition may be carried out in any known manners. For instance,
a dispense method and a compression molding method may be used.
On account of the properties such as excellent crack resistance,
heat resistance, light resistance and transparency, the present
curable resin composition and cured product are useful also as
materials for displays, optical recording mediums, optical
apparatus, optical components and optical fibers, and
photo/electron functional organic materials and materials for
integrated semiconductor circuit-related elements.
EXAMPLES
The present invention will be explained below in further detail
with reference to a series of the Examples and the Comparative
Examples, though the present invention is in no way limited by
these Examples.
In the following descriptions, the weight average molecular weight
(Mw) was determined by gel permeation chromatography, GPC, and
reduced to polystyrene. Conditions in the GPC were as follows.
[GPC Conditions]
Developing Solvent: Tetrahydrofuran
Flow rate: 0.6 mL/min.
Columns: all provided by TOSOH Cop.
TSK Guardcolumn SuperH-L
TSKgel SuperH4000 (6.0 mmI.D..times.15 cm.times.1)
TSKgel SuperH3000 (6.0 mmI.D..times.15 cm.times.1)
TSKgel SuperH2000 (6.0 mmI.D..times.15 cm.times.2)
Column Temperature: 40 degrees C.
Injection Volume: 20 micro liters of a 0.5% by mass solution in
tetrahydrofuran.
Detector: Differential refractive index detector (RI)
An amount of a vinyl (Vi) group (mol/100 g) and an amount of an SiH
group (mol/100 g) were calculated from an integrated area for
hydrogen atoms in .sup.1H-NMR spectra at 400 MHz with
dimethylsulfoxide as an internal standard. The .sup.1H-NMR spectra
was obtained with ULTRASHIELD.TM. 400PLUS, ex BRUKER
Corporation.
Components (A), (B) and (C) used in the following Examples and
Comparative Examples are as follows.
(A-1) Phenyl silicone resin which is represented by the following
formula, and has a Vi group content of 0.15 mol/100 g and a
weight-average molecular weight of 1,563, ex Shin-Etsu Chemical
Co., Ltd.:
##STR00028## wherein a ratio of n to m is 0.22:0.78. (A-2)
Silphenylene skeleton-containing silicone resin which is
represented by the following formula, and has a Vi group content of
0.19 mol/100 g and a weight-average molecular weight of 2,080, ex
Shin-Etsu Chemical Co., Ltd.:
##STR00029## wherein a ratio of n to m is 0.4:0.6. (A-3) Phenyl
silicone oil having vinyl groups at both terminals, which is
represented by the following formula, and has a Vi group content of
0.038 mol/100 g and a weight-average molecular weight of 5,729, ex
Shin-Etsu Chemical Co., Ltd.:
##STR00030## wherein a ratio of n to m is 0.03:0.97. (A-4) Phenyl
silicone oil having vinyl groups at both terminals, which is
represented by the following formula, and has a Vi group content of
0.038 mol/100 g and a weight-average molecular weight of 5,562, ex
Shin-Etsu Chemical Co., Ltd.:
##STR00031## wherein n is 38 on average. (A-5) Organic silicon
compound having vinyl groups at both terminals, which is
represented by the following formula, and has a Vi group content of
0.027 mol/100 g and a weight-average molecular weight of 7,433, ex
Shin-Etsu Chemical Co., Ltd.:
##STR00032## wherein a ratio of n to m is 0.67:0.33. (B-1)
Silphenylene skeleton-containing organic silicon compound which is
represented by the following formula, and has a SiH group content
of 1.2 mol/100 g and a weight-average molecular weight of 263, ex
Shin-Etsu Chemical Co., Ltd.:
##STR00033## (B-2) Silphenylene skeleton-containing organic silicon
compound which is represented by the following formula, and has a
SiH group content of 0.90 mol/100 g and a weight-average molecular
weight of 461, ex Shin-Etsu Chemical Co., Ltd.:
##STR00034## (B-3) Silphenylene skeleton-containing organic silicon
compound which is represented by the following formula, and has a
SiH group content of 0.78 mol/100 g and a weight-average molecular
weight of 667, ex Shin-Etsu Chemical Co., Ltd.:
##STR00035## (B-4) Silphenylene skeleton-containing organic silicon
compound which is represented by the following formula, and has a
SiH group content of 1.0 mol/100 g and a weight-average molecular
weight of 832, ex Shin-Etsu Chemical Co., Ltd.:
##STR00036## (B-5) Silphenylene skeleton-containing organic silicon
compound which is represented by the following formula, has a SiH
group content of 1.4 mol/100 g and a weight-average molecular
weight of 430, ex Shin-Etsu Chemical Co., Ltd.:
##STR00037## (B-6) Silphenylene skeleton-containing organic silicon
compound which is represented by the following formula, and has a
SiH group content of 1.3 mol/100 g and a weight-average molecular
weight of 1,140, ex Shin-Etsu Chemical Co., Ltd.:
##STR00038##
(B'-1) Organopolysiloxane which is represented by the following
formula, and has a SiH group content of 0.90 mol/100 g and a
weight-average molecular weight of 527, ex Shin-Etsu Chemical Co.,
Ltd.:
##STR00039##
(D-1) Silphenylene monomer which is represented by the following
formula, and has a SiH group content of 1.0 mol/100 g and a
weight-average molecular weight of 198, ex Shin-Etsu Chemical Co.,
Ltd.:
##STR00040##
(D-2) Linear organopolysiloxane having hydrosilyl groups at both
terminals, which is represented by the following formula, and has a
SiH group content of 0.61 mol/100 g and a weight-average molecular
weight of 341, ex Shin-Etsu Chemical Co., Ltd.:
##STR00041##
(D-3) Linear organopolysiloxane having hydrosilyl groups at both
terminals, which is represented by the following formula, and has a
SiH group content of 0.44 mol/100 g and a weight-average molecular
weight of 536, ex Shin-Etsu Chemical Co., Ltd.:
##STR00042##
(C) Divinylsiloxane complex of chloroplatinic acid containing 2
mass % of platinum, ex Shin-Etsu Chemical Co., Ltd.
Examples 1 to 8 and Comparative Examples 1 to 4
The aforesaid components except the catalyst were mixed in the
amounts as described in Tables 1 and, then, the catalyst (C) was
added in an amount, as a platinum metal, of 2 ppm relative to the
total mass of the composition, to obtain a curable resin
composition. The curable resin compositions prepared in Examples 1
to 8 and Comparative Examples 1 to 4 were evaluated according to
the following manners. The results are as shown in tables 2 and 3.
In table 1, the H/Vi is a ratio of the total number of the
hydrosilyl groups to the total number of the vinyl groups in the
composition.
[1. Viscosity of the Curable Resin Compositions]
The viscosity of the curable resin composition was determined with
a B-type viscometer at 23 degrees C. according to the Japanese
Industrial Standards (JIS) Z 8803:2011. The results are as shown in
Tables 2 and 3.
[2. Volatile and Nonvolatile Components in the Curable Resin
Compositions]
Approximately 1.5 grams of the curable resin composition was poured
into an aluminum petri dish having a diameter of 50 mm and a depth
of 10 mm and, then, heated at 150 degrees C. for 1 hours to obtain
a cured product. The masses before and after curing were precisely
measured. The masses of the volatile components and the nonvolatile
cured components were calculated from the masses before and after
heating. The volatile content and the nonvolatile content shown in
Tables 2 and 3 are percentages, relative to the amount of the
curable resin composition before heating.
[3. Hardness of the Cured Products]
The curable resin composition was poured into an aluminum petri
dish having a diameter of 50 mm and a depth of 10 mm and, then,
heated at 60 degrees C. for one hour, 100 degrees C. for one hour
and, subsequently 150 degrees C. for 4 hours to obtain a cured
product. A hardness of the cured product was determined with a
durometer type D according to the Japanese Industrial Standards
(JIS) K 6253-3:2012. The results are as shown in Tables 2 and
3.
[4. Light Transmittance of the Cured Products]
A U-shape Teflon (Trademark) spacer having a space of 40 mm width,
15 mm height and 1 mm depth was sandwiched between two glass slides
having dimensions of 50 mm.times.20 mm.times.1 mm at the both sides
of the spacer and they were tightly held. The curable resin
composition was poured into the space and heated at 60 degrees C.
for one hour, subsequently at 100 degrees C. for one hour and,
then, at 150 degrees C. for four hours, to obtain a cured sample
having thickness of 1 mm. A transmittance at 450 nm of the sample
was determined with a spectrophotometer, U-4100, ex Hitachi
High-Technologies Corporation. The results are as shown in Tables 2
and 3.
[5. Tensile Strength and Elongation at Break of the Cured
Products]
The curable resin composition was poured into a Teflon-coated mold
having a cavity of 150 mm.times.200 mm.times.2 mm, and heated
stepwise at 60 degrees C. for one hour, 100 degrees C. for one hour
and, subsequently 150 degrees C. for 4 hours to obtain a sample. A
tensile strength and an elongation at break of the cured product
were determined according to JIS K 6251:2010 with a tensile tester
EZ TEST, EZ-L, ex Shimadzu Corporation, in the following
conditions: a head speed was 500 mm/min, a distance between clamps
was 80 mm, and a distance of gauge points was 40 mm. The results
are as shown in Tables 2 and 3.
[6. Curing Rate]
The change of the storage elastic modulus G' in Pa of the curable
resin composition at 80 degrees C. with time was determined by a
testing apparatus, ALPHA TECHNOLOGIES APA 2000, and the value of
Tan .delta. derived from the obtained value of the storage elastic
modulus was plotted with time. The peak top time was read from the
graph and was taken as a gelation time. The measurement was carried
out at a frequency of 100 cpm and an amplitude angle of 0.750. The
results are as shown in Tables 2 and 3.
[7. Thermal Cycle Test]
The curable resin composition was dispensed on a Tiger3528 package,
ex Shin-Etsu Chemical Co., Ltd., and heated at 60 degrees C. for
one hour, 100 degrees C. for one hour and, subsequently 150 degrees
C. for 4 hours to cure. In this way, 20 sample packages
encapsulated with the cured product were obtained. The 20
encapsulated packages were subjected to a thermal cycle test (TCT)
with 1000 thermal cycles of from -50 degrees C. to 140 degrees C.
and then in a reversed way. The test samples which had cracks was
counted. The results are as shown in Tables 2 and 3.
TABLE-US-00001 TABLE 1 Com. Com. Com. Com. Ex. 1 Ex. 2 Ex. 3 Ex. 4
Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 1 Ex. 2 Ex. 3 Ex. 4 (A) (A-1) 80 80 80
50 50 50 80 80 80 80 (A-2) 70 50 (A-3) 20 20 20 30 50 20 20 20 20
(A-4) 50 50 (A-5) 50 (B) (B-1) 12.7 9.3 19.8 (B-2) 4.3 (B-3) 15.6
(B-4) 2.2 (B-5) 2.5 (B-6) 2.3 (B'-1) 8.3 9.3 6.5 (D) (D-1) 6.5
(D-2) 12.7 4.3 15.6 8.8 22.1 9.4 8.3 20.5 (D-3) 9.3 9.3 (C) 2 ppm
as platinum, relative to a total amount of the composition H/Vi 1 1
1.8 0.7 2.5 1.1 1.2 1.2 1 1 1 1
TABLE-US-00002 TABLE 2 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7
Ex. 8 Evaluation Viscosity 23 degrees C. Pa s 2.2 5.2 3.1 2.6 2 3.2
4 2.8 Nonvolatile 150 degrees % 99.6 99.4 99.5 99.6 99.8 99.8 99.7
99.8 content C., 1 hr Volatile 150 degrees % 0.4 0.6 0.5 0.4 0.2
0.2 0.3 0.2 content C., 1 hr Hardness Shore D -- 64 52 71 25 45 22
73 38 Transmittance thickness % T 99.7 99.7 99.6 99.8 99.6 99.7
99.7 99.6 of 1 mm, 450 nm Tensile 25 degrees C. MPa 12 6.7 22 3.3
5.4 3 26 4.4 strength Elongation 25 degrees C. % 60 70 30 150 100
160 30 120 at break Gelation 80 degrees C. min 4 6 2 5 4 5 5 5 time
Thermal 1000 thermal Number 0/20 0/20 0/20 0/20 0/20 0/20 0/20 0/20
cycle test cycles of -50 of the to/from 140 cracked degrees C.
samples
TABLE-US-00003 TABLE 3 Com. Com. Com. Com. Ex. 1 Ex. 2 Ex. 3 Ex. 4
Evaluation Viscosity 23 Pa s 5.6 5.8 5.8 5.5 degrees C. Nonvol- 150
% 99.7 99.3 97.2 99.7 atile degrees content C., 1 hr Volatile 150 %
0.3 0.7 2.8 0.3 content degrees C., 1 hr Hardness Shore D -- 50 42
35 55 Transmit- thickness % T 99.7 99.8 99.6 99.6 tance of 1 mm,
450 nm Tensile 25 MPa 5.6 3.2 2.6 7.5 strength degrees C.
Elongation 25 % 50 40 20 70 at break degrees C. Gelation 80 min 5 6
6 14 time degrees C. Thermal 1000 Number 15/20 16/20 20/20 0/20
cycle test thermal of the cycles cracked of -50 samples to/from 140
degrees C.
As shown in Table 3, the curable resin compositions of Comparative
Examples 1, 2 and 3 comprising the polyfunctional SiH type
organopolysiloxane having no silphenylene skeleton were excellent
in a curing rate, but inferior in mechanical strengths and showed
the poor crack resistance in the TCT test. In addition, the curable
resin composition of Comparative Example 3 comprising the
silphenylene monomer had the large volatile content derived from
the silphenylene monomer, which was deviated from the initial
composition, and the obtained cured product was brittle. In the
curable resin composition of Comparative Example 4 comprising the
silphenylene oligomer having only two SiH groups, the volatile
content was small and the crack resistance was excellent, but the
curability was inferior. On the other hand, the curable resin
composition of the present invention has the excellent curing rate
and quickly provides a cured product having excellent mechanical
strengths as shown in Examples 1 to 8.
The present curable resin composition comprising the organic
silicon compound which has the silphenylene skeleton and three or
more SiH groups has the excellent curing rate and provides a cured
product having the high toughness.
INDUSTRIAL APPLICABILITY
The curable resin composition of the present invention has the
excellent curability and the obtained cured product has the good
mechanical properties. Therefore, the curable resin composition of
the present invention is used, for example, for encapsulating a
semiconductor element to thereby improve its productivity. Further,
the curable resin composition gives a cured product having a high
optical transparency and an excellent mechanical strengths and,
therefore, is usable as a material for encapsulating an LED
element, in particular, a blue LED or an ultraviolet LED.
* * * * *